Nitrogen fluorine compounds and method of synthesis



United States Patent ABSTRACT OF THE DISCLOSURE This invention relatesto a novel process which comprises reacting anhydrous hydrazoic acidwith a compound having the formula wherein R and R are, individually, NNF F or -NF|C-NF radicals, in the presence of a catalytic amount of anitrogen containing material, and the compounds produced thereby. Stillmore particularly, this invention relates to a process which comprisesreacting the product produced by reacting hydrazoic acid with a compoundrepresented by Formula I, with fluorine gas, and the products producedthereby.

The process of the present invention proceeds according to the equationwherein R and R are as defined above and R and R are, individually, N NFor N-F 1i radicals.

As mentioned above, the reaction is carried out in the presence of anitrogen containing catalyst. Examples of such materials includetrialkyl amines such as trimethyl amine, triethyl amine, tributyl amine,etc., cyclic compounds such as pyridine, quinoline, isoquinoline, apicoline, pyrazine, pyrimidine, acridine, 1,4 diazabicyclo [2,2,2]octaneand the like. The catalyst concentration in the solvent ranges fromabout 0.001 mole percent to about 5 mole percent, preferably from about0.01 mole percentfto about 1 mole percent.

Temperatures ranging from about -140 to about 50 C., preferably fromabout 111 to 25 C., may be used.

Solvents such as fluorochlorocarbon materials, i.e., CFCI fluorocarbonoils, CHFCl Cl CF--(CFCl) CCl F and the like must also be employedduring the reaction.

3,405,143 Patented Oct. 8, 1968 ice The starting materials, i.e., thoseof Formula I are produced by direct fluorination of the correspondinghydrogen derivative by methods well known to those skilled in the art.

, Examples offithe novel compounds of Formula II, pro- 7 duced hereinand useful as intermediates for the production of further novelcompounds according to a second aspect of the instant invention,include:

As mentioned above, these compounds are useful as intermediates for theproduction of compounds containing higher concentrations of nitrogen andfluorine. This second novel class of compounds is produced according tothe equation:

wherein R and R are as defined above and R and R are, individually, N NFF or 1]? N3 -N( |JNF2 NFz radicals.

This reaction is conducted at about 40 C. to about C., preferably about---25 to about 50 C., i.e., in

the vapor phase, with a molar excess of fluorine gas to startingmaterial, i.e., that of Formula II.

The compounds represented by Formula III find use as oxidizers in rocketpropellant compositions and also as intermediates for the production ofadditional compounds through reaction with the azide group thereof.Examples of compounds represented by Formula III include The vessel isattached to 4 a vacuum line, evacuated and cooled to 111 C. 0.048 partof pyridine, 149 parts of perfiuoroguanidine [(NF C NF] and 43 parts ofhydrazoic acid are charged to the vessel which is then allowed to warmto room temperature. Stirring is started when the temperature reaches--40 C. After /2 hour the resultant reaction mixture is vacuum strippedat N; NF: F Na F Na I l C. 172.8 parts ofb1s(d1fluoroam1no)fiuoroannnomethyl C NF NFZTC N C NF azide arerecovered in a U-trap at 111 C. The azide is N3 N3 NF2 N3 F Na NF; N-F10 a colorless liquid and very sensitive to shock. It has the followingproperties.

ir Vapor pressure: mm. at 24 C. N3 NFz Boihng point: -90 C.

\ P NMR:

t F r' ff N F NF at 24.9 broad. 7 7 NF: Na F "Na a NHF at 128.7 5,doublet split by -56 cps.

NF NF: H'NMR: Two broad peaks centered at +1.42T, split by I r ti Sh b dh'h d N n rare ows an s w 1c are assigne to e F --NI-IF and NF groups. F-C-N-F N C-NF N N 3 3 Following the procedure of Example 2, variousother NF! NF? NF? materials are reacted with hydrazoic acid according tothe and the like. instant invention. The results are set forth in TableI,

The following examples are set forth for purposes of below.

TABLE I Ex. Formula I compound Solvent Catalyst T errp Product producedN312 NF; H 3 C=N-F CFCls Trietliyl amine- 50 CN l F F Na F e n 4 /C=NFCHFClz"-.--- a-Pieoline 25 (Na):Cl [I-H e t 5 N32 /C=NF Same as Ex. 2.Pyridine -10 FzN-C|}N(f-NF /C'N F N? F H F H F\ F\ /H 6 G'=NF CFClsQulnoline -11l C-N I F F N: F

Removed from product by vacuum stripping at -20 C.

illustration only and are not to be construed as limiting EXAMPLE 7 theinstant invention except as set forth in the appended claims. All partsand percentages are by weight unless otherwise specified.

EXAMPLE 1 (Preparation of hydrazoic acid) EXAMPLE 2 Into a suitablereaction vessel containing a magnetic stirring bar are charged 10,000parts of Into a suitable apparatus composed of three U-tubes connectedin series by ball joints are condensed at 111 0, into the first tube,100 parts of bis(difluoroamino) fluoraminomethyl azide. Liquid nitrogenbaths are placed around the second and third tubes. The first tube isallowed to warm to C. and gas streams of helium and fluorine, at a spacevelocity of 50 cc./min. and 16 cc./min., respectively, are passedthrough the series of tubes. After 20 minutes, no liquid azide remainsin the first tube. The last two tubes are isolated, evacuated and warmedto l11 C. The volatiles are removed and the remaining material is passedthrough a trap at 30 C. and collected at 196 C. 94.5 parts oftris(difluoroamino)methyl azide are recovered. P NMR shows a singlebroad band at -28.7. The estimated boiling point is 60 C. The infraredspectrum shows bands which are assigned to N and NF groups.

Following the procedure of Example 7, various other materials arefluorinated according to the instant invention. The results are setforth in Table II, below.

TABLE II Ex. Formula II compound Tgnp Product produced 8 NFa H 100 NF:

G--N G-NFn F I Ia F F L TB NF: 9...-- (NQr--N-H 0 a)r- 2)2 N; F Na Na a10-..- FzN-C 3-NCNFg 60 (FzNh--N--(NFM 1k 1 1 F H F H F' 11-.-- F H -40F C-N CNF2 F l l'a F F l l's We claim: 1. A compound having the formulaC--N R6113 H wherein R and R are, individually, selected from the groupconsisting of N N1 F and 3. A method for the production of the compoundof 6 claim 1 which comprises reacting hydrazoic acid with a compoundhaving the formula wherein R and R are, individually, selected from thegroup consisting of N NF F and -NF'(HJNFg radicals.

5. A compound according to claim 4, wherein R and R are NF radicals.

References Cited UNITED STATES PATENTS 3,226,439 12/1965 Middleton260-349 XR 3,228,936 1/1966 Davis et al. 260-564 XR 3,278,595 10/1966Sheehan et a1. 149-409 XR OTHER REFERENCES Mitsch: J. Am. Chem. Soc.,vol. 87, 1965, pp. 328333.

HENRY R. JILES, Primary Examiner.

C. M. SHURKO, Assistant Examiner.

